WO2020251472A1 - Matériau de cathode et procédé de préparation de celui-ci - Google Patents

Matériau de cathode et procédé de préparation de celui-ci Download PDF

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WO2020251472A1
WO2020251472A1 PCT/SG2020/050319 SG2020050319W WO2020251472A1 WO 2020251472 A1 WO2020251472 A1 WO 2020251472A1 SG 2020050319 W SG2020050319 W SG 2020050319W WO 2020251472 A1 WO2020251472 A1 WO 2020251472A1
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cathode material
sulfur
cathode
range
conducting carbon
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PCT/SG2020/050319
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English (en)
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Jackie Y. Ying
Jian Liang CHEONG
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Agency For Science, Technology And Research
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Priority to US17/618,832 priority Critical patent/US20220293946A1/en
Publication of WO2020251472A1 publication Critical patent/WO2020251472A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a cathode material, a method of preparing the same, an electrochemical cell and a lithium-sulfur battery.
  • Li-S battery system very attractive for energy storage.
  • Li-S batteries Although already in the market for niche applications, full-scale commercialization of Li-S batteries will not be realized until certain challenges are overcome. These problems are largely related to the cathode: low active material utilization due to low electronic conductivity of sulfur and Li 2 S, collapse of cathode structure from the constant volume changes during cycling, and polysulfide (PS) shuttling effect leading to poor cycling stability.
  • PS polysulfide
  • the Li-S battery has an intricate electrochemistry.
  • PS Since sulfur dissolution to PS is inevitable, PS has been considered to be used as a sulfur source for Li-S batteries or the cathode structure and the way of sulfur loading may be modified to increase sulfur loading and to address the PS shutting effect. In fact, it has been shown that the use of PS in place of solid sulfur as cathode material offers several advantages, such as improved sulfur utilization and enhanced redox kinetics. Earlier work on Li-PS batteries established that PS cathodes have reduced polarization, high ionic conductivity and high capacity retention, as compared to solid sulfur cathodes.
  • slurry-coated PS electrodes such as Pt/graphene, Super P® carbon black, silica-etch carbon, metal nitrides and hierarchical porous carbon.
  • These materials have either low electronic conductivity (Super P® carbon blackand silica-etch carbon) or small surface area (Super P® carbon black and metal nitride nanoparticles).
  • the Pt/graphene material is expected to work well, its cathode microstructure appear less porous and too dense. Thus, PS interaction with active Pt/graphene surface would not be optimal for electrochemical performance.
  • the present disclosure relates to a cathode material comprising a layer of sulfur species dispersed within or thereon a porous matrix comprising a first conducting carbon material, a second conducting carbon material and a binder, wherein the second conducting carbon material is carbon fiber or carbon nanotube.
  • the present disclosure relates to a cathode material comprising a layer of sulfur species dispersed within or thereon a porous matrix comprising a first conducting carbon material, a second conducting carbon material and a binder, wherein said porous matrix is interconnected with uniform pores.
  • the cathode material may be interconnected with pores that are uniform in size and volume, large surface area and/or small ohmic resistance.
  • the cathode material as described herein can be used in a lithium-sulfur battery and due to the large surface area, availability of electrochemically active sites for sulfur species, such as sulfur (S), lithium sulfide (Li 2 S) and polysulfide (PS), can be increased, allowing both nucleation and binding to occur on the cathode surface, leading to higher specific capacities of the cathode material.
  • the large surface area of the cathode material as described herein may lead to a decrease in the concentration of dissolved PS in bulk, reducing the undesired PS shuttling effect. Therefore, the capacity fading of the capacity fading of the electrode material may be inhibited.
  • the present disclosure relates to a method for preparing a cathode material comprising the steps of:
  • the present disclosure relates to a method for preparing a cathode material comprising the steps of:
  • the coated support by forming the coated support first and then adding the sulfur species onto the coated support, this results in the final cathode material that is interconnected with pores that are of uniform size and volume.
  • the final cathode material may also have a large surface area as well as a smaller ohmic resistance. Therefore, the steps in the method have to be in this order whereby the cathode material is preformed, followed by dispersion of the sulfur source therein or thereon. This is in comparison to melt-diffusion methods in which the sulfur source is added to the support first, followed by the cathode material and the binder. Using melt-diffusion results in a cathode with inconsistent pore sizes.
  • the method as described herein by slurry coating may utilize inexpensive commercially available materials to develop high-performance lithium-PS batteries with large- surface-area cathodes as compared to conventional melt -diffusion method.
  • the method as described herein is industrially scalable and environmentally friendly.
  • the cathode preparation method has a strong influence on the electrochemical performance, different cathode preparation approaches should be considered for future designs of practical lithium-sulfur batteries.
  • the present disclosure relates to a cathode material prepared by the method as described herein.
  • the present disclosure relates to an electrochemical cell comprising a cathode material as described herein and a liquid electrolyte.
  • the present disclosure relates to a lithium-sulfur battery comprising one or more electrochemical cells as described herein.
  • the lithium-sulfur battery as described herein high specific capacities between 1220 mAh g 1 and 1007 mAh g 1 can be achieved at charge rates of 0.2-2.0 C, with low capacity fade of lower than 0.14% per cycle over 200 cycles. At higher sulfur loading, a practical areal capacity of > 4 mAh g 1 can also be achieved.
  • the cathode material as described herein may offer 48% higher specific capacity and 26% lower capacity fade than the sulfur cathode prepared by the conventional melt-diffused method due to differences in morphology, surface area and ohmic resistance of the cathodes.
  • interconnected or“interconnectivity” as used here represents the characteristics of the cathode material that maintains unimpeded electronic pathways from current collector throughout the entire cathode structure during the charging and/or discharging operation of the sulfur -lithium battery, and therefore achieves good conductivity and low ohmic resistance of the cathode material.
  • polysulfide represents a class of chemical compounds comprising chains of sulfur atoms.
  • the chain of sulfur atoms may have the general formal S n 2 and may be a conjugate base to form a compound with metal ions, such as lithium or sodium.
  • graphene represents a two-dimensional allotrope of carbon in the form of a single layer of atoms with the carbon atoms arranged in a two-dimensional honeycomb lattice.
  • the tern’’reduced graphene oxide is one form of graphene oxide that is processed by chemical, thermal and other methods in order to reduce the oxygen content.
  • the term "about”, in the context of concentrations of components of the formulations, typically means +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value.
  • range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub -ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
  • the present disclosure relates to a cathode material comprising a layer of sulfur species dispersed within or thereon a porous matrix comprising a first conducting carbon material, a second conducting carbon material and a binder, wherein the second conducting carbon material is carbon fiber or carbon nanotube.
  • the present disclosure relates to a cathode material comprising a layer of sulfur species dispersed within or thereon a porous matrix comprising a first conducting carbon material, a second conducting carbon material and a binder, wherein said porous matrix is interconnected with uniform pores.
  • the sulfur species may be a polysulfide or elemental sulfur.
  • the layer of sulfur species may be a continuous layer of sulfur particles.
  • the layer of sulfur species may be polysulfide molecules.
  • the polysulfide molecules may be adsorbed onto the porous matrix through electrostatic or polar-polar interactions.
  • the polysulfide may have a formula of Li 2 S n , wherein 2 ⁇ n ⁇ 8.
  • the polysulfide may be selected from Li 2 S 2 , Li 2 S 4 , Li 2 S 6 , Li 2 S 8 or their mixtures thereof.
  • the polysulfide may preferably be Li 2 S 6 -
  • the cathode material may have a sulfur content in the range of about 30 wt% to about 80 wt%, about 35 wt% to about 80 wt%, about 40 wt% to about 80 wt%, about 45 wt% to about 80 wt%, about 50 wt% to about 80 wt%, about 55 wt% to about 80 wt%, about 60 wt% to about 80 wt%, about 65 wt% to about 80 wt%, about 70 wt% to about 80 wt%, about 75 wt% to about 80 wt%, about 30 wt% to about 75 wt%, about 30 wt% to about 70 wt%, about 30 wt% to about 65 wt%, about 30 wt% to about 60 wt%, about 30 wt% to about 55 wt%, about 30 wt% to about 50 wt%, about 30 wt% to about 45 wt%,
  • the first conducting carbon material may be selected from the group consisting of reduced graphene oxide, graphene, graphite, carbon nanotube, carbon fiber, acetylene black, and ketjenblack.
  • the first conducting carbon material may be different from the second conducting carbon material. Specifically, where the second conducting material is carbon nanotube, the first conducting material is not carbon nanotube. Specifically, where the second conducting material is carbon fiber, the first conducting material is not carbon fiber.
  • the first conducting carbon material may be reduced graphene oxide (rGO).
  • the first conducting carbon material may be doped with nitrogen, oxygen, sulfur, boron, phosphorus or their mixtures thereof.
  • Advantageously reduced graphene oxide (rGO) doped with nitrogen is highly conductive.
  • the sites of doped nitrogen, oxygen, sulfur, boron, pohosphorus or their mixtures thereof have high affinity for polysulfide absorption to mitigate polysulfide shuttling.
  • the amount of the first conducting material may be in the range of about 20 wt% to about 60 wt%, about 25 wt% to about 60 wt%, about 30 wt% to about 60 wt%, about 35 wt% to about 60 wt%, about 40 wt% to about 60 wt%, about 45 wt% to about 60 wt%, about 50 wt% to about 60 wt%, about 55 wt% to about 60 wt%, about 20 wt% to about 55 wt%, about 20 wt% to about 50 wt%, about 20 wt% to about 45 wt%, about 20 wt% to about 40 wt%, about 20 wt% to about 35 wt%, about 20 wt% to about 30 wt % or about 20 wt% to about 25 wt % based on the total weight of the cathode material.
  • the binder may be a copolymer of acrylamide, lithium carboxylate and cyano group, polyvinylidene fluoride (PVDF), styrene/butadiene copolymer (SBR), carboxylmethyl cellulose (CMC), polysaccharides, or a polymer having a monomer selected from the group consisting of olefin, butadiene, carboxylate, carboxylate salt of Li and Na, styrene, amide, ester, acrylate, methacrylate, urethane and mixtures thereof.
  • the binder may preferably be a copolymer of acrylamide, lithium carboxylate and cyano group, an example of which is LA- 132 from Chengdu Indigo Power Sources Co. Ltd. (China).
  • the binder may be water soluble.
  • the binder may be water-soluble LA-132 binder, which is non-toxic as compared to the conventional PVDF/N-methyl-2-pyrrolidone (NMP) binder/solvent system.
  • the amount of the binder may be in the range of about 5 wt% to about 15 wt%, about 6.5 wt% to about 15 wt%, about 8 wt% to about 15 wt%, about 9.5 wt% to about 15 wt%, about 11 wt% to about 15 wt%, about 12.5 wt% to about 15 wt%, about 14 wt% to about 15 wt%, about 5 wt% to about 14 wt%, about 5 wt% to about 12.5 wt%, about 5 wt% to about 11 wt%, about 5 wt% to about 9.5 wt%, about 5 wt% to about 8 wt% or about 5 wt% to about 6.5 wt% based on the total weight of the cathode material.
  • the first conducting carbon material and the second conducting carbon material are placed or supported on a support. Flaving a binder in the slurry and therefore in the resultant cathode results in the cathode being bound together, where the binding occurs between the polysulfide, the first conducting carbon material and the second conducting carbon material and/or between the first conducting carbon material, the second conducting carbon material and the support. This differentiates the cathode material from the ‘free-standing’ cathode material of the prior art. Functional groups on the binder may impart polysulfide trapping properties and also enhance ionic conduction.
  • the carbon fiber material may impart mechanical strength to the cathode structure.
  • the second conducting carbon material may have a diameter in the range of about 0.1 nm to about 100 pm, about 1 nm to about 100 pm, about 10 nm to about 100 pm, about 100 nm to about 100 pm, about 1 pm to about 100 pm, about 10 pm to about 100 pm, about 0.1 nm to about 10 pm, about 0.1 nm to about 1 pm, about 0.1 nm to about 100 nm, about 0.1 nm to about 10 nm, about 0.1 nm to about 1 nm.
  • the carbon fiber material may be vapor grown carbon fiber (VGCF).
  • the second conducting carbon material may be functionalized with functional groups to further impart polysulfide trapping properties and enhance ionic conduction.
  • functional groups are -OH, - COOH, -NH 2 , -SH or -S0 2 H.
  • the amount of the second conducting carbon material may be in the range of about 5 wt% to about 35 wt%, about 10 wt% to about 35 wt%, about 15 wt% to about 35 wt%, about 20 wt% to about 35 wt%, about 25 wt% to about 35 wt%, about 30 wt% to about 35 wt%, about 5 wt% to about 30 wt%, about 5 wt% to about 25 wt%, about 5 wt% to about 20 wt%, about 5 wt% to about 15 wt% or about 5 wt% to about 10 wt% based on the total weight of the cathode material.
  • the first conducting carbon material, the binder and the second conducting carbon material may be inexpensive and commercially available material that are easy to be produced on an economical scale.
  • the cathode material as described herein may have a sulfur loading density in the range of about 1.3 mg cm -2 to about 15 mg cm -2 , about 1.5 mg cm -2 to about 15 mg cm -2 , about 2 mg cm -2 to about 15 mg cm -2 , about 2.5 mg cm -2 to about 15 mg cm -2 , about 3 mg cm -2 to about 15 mg cm -2 , about 5 mg cm -2 to about 15 mg cm -2 , about 7 mg cm -2 to about 15 mg cm -2 , about 9 mg cm -2 to about 15 mg cm -2 , about 11 mg cm -2 to about 15 mg cm -2 , about 13 mg cm -2 to about 15 mg cm -2 , about 1.3 mg cm -2 to about 13 mg cm -2 , about 1.3 mg cm -2 to about 11 mg cm -2 , about 1.3 mg cm -2 to about 9 mg cm -2 , about 1.3 mg cm -2 to about 7 mg cm -2 , about 1.3 mg cm -2 to about 5 mg cm -2 , about
  • the cathode material may have a charge transfer resistance in the range of about 2 W to about 50 W, about 5 W to about 50 W, about 10 W to about 50 W, about 15 W to about 50 W, about 20 W to about 50 W, about 25 W to about 50 W, about 30 W to about 50 W, about 35 W to about 50 W, about 40 W to about 50 W, about 45 W to about 50 W, about 2 W to about 45 W, about 2 W to about 40 W, about 2 W to about 35 W, about 2 W to about 30 W, about 2 W to about 25 W, about 2 W to about 20 W, about 2 W to about 15 W, about 2 W to about 10 W, about 2 W to about 5 W as characterized by electrochemical impedance spectroscopy (EIS).
  • EIS electrochemical impedance spectroscopy
  • the cathode material as described herein may have a surface area in the range of about 200 m 2 /g to about 900 m 2 /g, about 250 m 2 /g to about 900 m 2 /g, about 300 m 2 /g to about 900 m 2 /g, about 350 m 2 /g to about 900 m 2 /g, about 400 m 2 /g to about 900 m 2 /g, about 450 m 2 /g to about 900 m 2 /g, about 500 m 2 /g to about 900 m 2 /g, about 550 m 2 /g to about 900 m 2 /g, about 600 m 2 /g to about 900 m 2 /g, about 650 m 2 /g to about 900 m 2 /g, about 700 m 2 /g to about 900 m 2 /g, about 750 m 2 /g to about 900 m 2 /g, about 800
  • the cathode material as described herein may have a pore volume in the range of about 0.25 cm 3 /g to about 3 cm 3 / g, about 0.5 cm 3 / g to about 3 cm 3 / g, about 1 cm 3 / g to about 3 cm 3 / g, about 1.5 cm 3 / g to about 3 cm 3 /g, about 2 cm 3 / g to about 3 cm 3 /g, about 2.5 cm 3 / g to about 3 cm 3 /g, about 0.25 cm 3 / g to about 2.5 cm 3 /g, about 0.25 cm 3 / g to about 2 cm 3 /g, about 0.25 cm 3 / g to about 1.5 cm 3 /g, about 0.25 cm 3 /g to about 1 cm 3 /g or about 0.25 cm 3 /g to about 0.5 cm 3 /g.
  • the cathode material as described herein may have a pore size distrbution of mesopore size in the range of about 2 nm to about 50 nm and macropore size more than 50 nm
  • the mesopore size may be in the range of about 2 nm to about 50 nm, about 5 nm to about 50 nm, about 10 nm to about 50 nm, about 15 nm to about 50 nm, about 20 nm to about 50 nm, about 25 nm to about 50 nm, about 30 nm to about 50 nm, about 35 nm to about 50 nm, about 40 nm to about 50 nm, about 45 nm to about 50 nm, about 2 nm to about 45 nm, about 2 nm to about 40 nm, about 2 nm to about 35 nm, about 2 nm to about 30 nm, about 2 nm to about 25 nm, about 2 nm to about 20 nm, about 2 nm to about 15 nm, about 2 nm to about 10 nm or about 2 nm to about 5 nm.
  • the porous matrix of the cathode material is interconnected with uniform pores as compared to the structure of conventional cathode materials.
  • Pore uniformity and cathode interconnectivity may impart mechanical and electrical stability of the electrode, which contribute to the high retention capability of the lithium- sulfur battery.
  • the interconnected structure allows unimpeded electronic pathways from current collector throughout the entire structure.
  • the uniformity and interconnectivity also contribute to the high surface area and low ohmic resistance of the cathode, which are crucial factors to achieve high specific capacities of the lithium- sulfur battery.
  • the cathode material whereby the porous matrix contains carbon fiber or carbon nanotube as the second conducting carbon material, can be regarded as being interconnected with uniform pores.
  • the present disclosure relates to a method for preparing a cathode material comprising the steps of: a) coating a support with a slurry formed by mixing a mixture of a first conducting carbon material, a second conducting carbon material and a binder, wherein the second conducting carbon material is carbon fiber or carbon nanotube; and
  • the present disclosure relates to a method for preparing a cathode material comprising the steps of: a) coating a support with a slurry formed by mixing a mixture of a first conducting carbon material, a second conducting carbon material and a binder; and
  • the second conducting carbon material may improve the mechanical strength and interconnectivity of the coated support formed.
  • the method may further comprise, before said coating step (a), the step of (al) stirring said mixture in a solvent overnight with a solid content in the range of 3 wt% to 10 wt%.
  • the solvent may be water or water mixture with polar organic solvents.
  • polar organic solvents may be ethanol, isopropyl alcohol, butanol, N-methyl-2-pyrrolidone or their mixtures thereof.
  • the first conducting material may have a concentration in the range of about 60 wt% to about 90 wt%, about 65 wt% to about 90 wt%, about 70 wt% to about 90 wt%, about 75 wt% to about 90 wt%, about 80 wt% to about 90 wt%, about 85 wt% to about 90 wt%, about 60 wt% to about 85 wt%, about 60 wt% to about 80 wt%, about 60 wt% to about 75 wt%, about 60 wt% to about 70 wt% or about 60 wt% to about 65 wt% based on the total weight of solid content in the slurry.
  • the first conducting carbon material may be selected from the group consisting of reduced graphene oxide, graphene, graphite, carbon nanotube, carbon fiber, acetylene black, and ketjenblack.
  • the first conducting carbon material may be different from the second conducting carbon material. Specifically, where the second conducting material is carbon nanotube, the first conducting material is not carbon nanotube. Specifically, where the second conducting material is carbon fiber, the first conducting material is not carbon fiber.
  • the first conducting carbon material may be reduced graphene oxide (rGO).
  • the second conducting carbon material may have a concentration in the range of about 5 wt% to about 50 wt%, about 10 wt% to about 50 wt%, about 15 wt% to about 50 wt%, about 20 wt% to about 50 wt%, about 25 wt% to about 50 wt%, about 30 wt% to about 50 wt%, about 35 wt% to about 50 wt%, about 40 wt% to about 50 wt%, about 45 wt% to about 50 wt%, about 5 wt% to about 45 wt%, about 5 wt% to about 40 wt%, about 5 wt% to about 35 wt%, about 5 wt% to about 30 wt%, about 5 wt% to about 25 wt%, about 5 wt% to about 20 wt%, about 5 wt% to about 15 wt% or about 5 wt% to about 10 wt % based
  • the binder may have a concentration in the range of about 5 wt% to about 20 wt%, about 10 wt% to about 20 wt%, about 15 wt% to about 20 wt%, about 5 wt% to about 15 wt% or about 5 wt% to about 10 wt% based on the total weight of solid content.
  • the mass ratio of the conducting material versus the carbon fiber material may be in the range of about 1 : 1 to 10: 1.
  • the mass ratio of the carbon fiber material versus the binder may be in the range of 1 : 2 to 2:1.
  • the mass ratio of the carbon fiber material versus the binder may preferably be 1 : 1.
  • the mixture may be applied on the support via the doctor’s blade method.
  • a solid mass in the range of about 3 mg to 4 mg may be used to prepare the cathode material as described herein for use in a coin cell. Larger amount of the solid mass is required in proportion if the cathode material is used in a larger lithium-sulfur battery.
  • the method as described herein may further comprise, after said coating step (a), the step of (a2) drying the coated support at a temperature in the range of about 40 °C to about 80 °C, about 50 °C to about 80 °C, about 60 °C to about 80 °C, about 70 °C to about 80 °C, about 40 °C to about 70 °C, about 40 °C to about 60 °C or about 40 °C to about 50 °C for more than 2 hours, more than 4 hours, more than 6 hours, more than 8 hours, more than 10 hours, more than 12 hours, more than 14 hours or more than 16 hours or more than 18 hours after coating the support with the slurry.
  • the drying step may preferably in the range of about 60°C to about 80°C.The drying step may be done overnight.
  • the method as described herein may comprise the step of preparing a polysulfide (PS) solution as the sulfur source in fluid state by stirring a mixture of sulfur (S) and lithium sulfide (Li 2 S).
  • PS polysulfide
  • the mixture may be stirred at a temperature in the range of about 40°C to about 60°C overnight in a glovebox.
  • the glovebox may be filled with an inert gas due to high reactive of lithium and to prevent other unnecessary side reactions.
  • the glovebox may be Argon filled.
  • the polysulfide may have a formula of Li 2 S n , wherein 2 ⁇ n ⁇ 8.
  • the polysulfide may be selected from Li 2 S 4 , Li 2 S 6 , Li 2 S 8 or their mixtures thereof.
  • the polysulfide may preferably be Li 2 S 6 -
  • the sulfur (S) and the lithium sulfide (Li 2 S) may be mixed in an electrolyte as solvent.
  • the electrolyte may be an electrolyte known in the art commonly used for a lithium-sulfur battery.
  • the electrolyte may be prepared by adding about 0.5 M to about 3 M LiTFSI, LiOTf, LiFSI or LiBETI and about 0.1 wt% to about 10 wt% LiN0 3 to a mixture of 1,3-dioxolane (DOL) and 1,2 -dime thoxye thane (DME) (volume ratio in the range of about 3: 1 to about 1 :3).
  • DOL 1,3-dioxolane
  • DME 1,2 -dime thoxye thane
  • the concentration of the sulfur in the mixture may be in the range of about 50 mg/mL to about 200 mg/mL, about 70 mg/mL to about 200 mg/mL, about 80 mg/mL to about 200 mg/mL, about 100 mg/mL to about 200 mg/mL, about 120 mg/mL to about 200 mg/mL, about 140 mg/mL to about 200 mg/mL, about 160 mg/mL to about 200 mg/mL, about 180 mg/mL to about 200 mg/mL, about 50 mg/mL to about 180 mg/mL, about 50 mg/mL to about 160 mg/mL, about 50 mg/mL to about 140 mg/mL, about 50 mg/mL to about 120 mg/mL, about 50 mg/mL to about 100 mg/mL, about 50 mg/mL to about 80 mg/mL, about 50 mg/mL to about 70 mg/mL.
  • the concentration of the lithium sulfide (Li 2 S) in the mixture may be in the range of about 10 mg/mL to about 60 mg/mL, about 20 mg/mL to about 60 mg/mL, about 30 mg/mL to about 60 mg/mL, about 40 mg/mL to about 60 mg/mL, about 50 mg/mL to about 60 mg/mL, about 10 mg/mL to about 50 mg/mL, about 10 mg/mL to about 40 mg/mL, about 10 mg/mL to about 30 mg/mL, about 10 mg/mL to about 20 mg/mL.
  • the mixture may have a S/Li 2 S mass ratio in the range of about 2: 1 to about 5: 1.
  • the S/Li 2 S mass ratio may preferably be 3.5: 1.
  • the polysulfide (PS) solution may have a sulfur concentration in the range of about 2.0 M to about 6.0 M, about 2.5 M to about 6.0 M, about 3.0 M to about 6.0 M, about 3.5 M to about 6.0 M, about 4.0 M to about 6.0 M, about 4.5 M to about 6.0 M, about 5.0 M to about 6.0 M, about 5.5 M to about 6.0 M, about 2.0 M to about 5.5 M, about 2.0 M to about 5.0 M, about 2.0 M to about 4.5 M, about 2.0 M to about 4.0 M, about 2.0 M to about 3.5 M, about 2.0 M to about 3.0 or about 2.0 M to about 2.5 M.
  • the method as described herein may comprise the step of obtaining the sulfur source in fluid state by heating elemental sulfur solid at a temperature in the range of about 160°C to about 190°C, about 170°C to about 190°C, about 180°C to about 190°C, about 160°C to about 180°C or about 160°C to about 170°C.
  • the duration of the heating step may be in the range of about 5 minutes to about 40 minutes, about 10 minutes to about 40 minutes, about 15 minutes to about 40 minutes, about 20 minutes to about 40 minutes, about 25 minutes to about 40 minutes, about 30 minutes to about 40 minutes, about 35 minutes to about 40 minutes, about 5 minutes to about 35 minutes, about 5 minutes to about 30 minutes, about 5 minutes to about 25 minutes, about 5 minutes to about 20 minutes, about 5 minutes to about 15 minutes or about 5 minutes to about 10 minutes,.
  • the present disclosure relates to a cathode material prepared by the method as described herein.
  • the present disclosure relates to an electrochemical cell comprising a cathode material as described herein and a liquid electrolyte.
  • the electrolyte may be an electrolyte known in the art commonly used for a lithium-sulfur battery.
  • the electrolyte may be prepared by adding 1 M LiTFSI and 2 wt% LiN0 to a mixture of 1,3-dioxolane (DOL) and 1,2 -dime thoxy ethane (DME) (volume ratio of 1 : 1).
  • the present disclosure relates to a lithium-sulfur battery comprising one or more electrochemical cells as described herein.
  • the cathode material may have more than 82% capacity retained over 200 cycles or an average capacity fade of about 0.09% per cycle (see examples below). At a higher sulfur loading of 5.05 mg cm 2 , the cathode material as described herein may attain a practical areal capacity of > 4 mAh cm 2 over 50 cycles.
  • the cathode material as described herein may give a 48% higher specific capacity and 26% lower capacity fade, as compared to conventional cathode prepared by melt-diffusion method. This difference could be attributed to the difference in morphology, surface area and Ohmic resistance, factors which are strongly influenced by how the cathodes are being prepared.
  • FIG. 1 is a schematic diagram showing the preparation of the cathode material as described herein ( Figure 1A) and the cathode material prepared by the conventional melt-diffusion method ( Figure IB).
  • FIG. 2 shows SEM images under 5000x magnification of preforemd rGO cathodes before PS addtion: top view ( Figure 2a) and cross-sectional view ( Figure 2b).
  • FIG. 3 shows SEM image under 500x magnification of a preformed rGO cathode with elemental mapping: (Figure 3a) SEM image, and ( Figure 3b) C, ( Figure 3c) N, and ( Figure 3d) O maps of preformed rGO cathode.
  • Figure 4 is a number of graphs showing the electrochemical Performance of PS/rGO cathode.
  • FIG. 5 is a graph showing the specific capacities of PS/rGO cathode and S(vapor)/rGO cathode prepared by sulfur vapor deposition.
  • FIG. 6 is a graph showing rate capability studies of PS/rGO and S/rGO cathodes at a S loading of 1.50 mg cm 2 .
  • FIG. 7 is a number of graphs showing long-term cycling performance of PS/rGO and S/rGO cathodes at (a) 0.2 C, (b) 0.5 C, (c) 1.0 C and (d) 2.0 C with a S loading of 1.50 mg cm 2 .
  • Figure 8 shows SEM images of PS/rGO cathode (Figure 8a, b) before and (Figure 8c, d) after rate capability studies.
  • Figures 8a and 8c are under lOOOx magnification
  • Figures 8b and 8d are under 5000x magnification.
  • Figure 9 shows SEM images of S/rGO cathode (Figure 9a, b) before ( Figure 9c, d) after rate capability studies.
  • Figures 9a and 9c are under lOOOx magnification
  • Figures 9b and 9d are under 5000x magnification.
  • Figure 10 is a number of graphs showing nitrogen adsorption which was performed on PS/rGO or S/rGO cathodes in the absence of sulfur or Fi-PS.
  • Figure 10a Nitrogen adsorption/desorption isotherm.
  • Figure 10b BJH desorption pore size distribution of of PS/rGO and S/rGO.
  • FIG. 11 is a graph showing cyclic voltammograms of PS/rGO and S/rGO cathodes.
  • Figure 12 is a graph showing Nyquist plots of cycled PS/rGO and S/rGO cells after rate capability studies.
  • the inset shows a high-frequency region with electrochemically fitted circuit.
  • a slurry-coated method 10 of forming a cathode material 600 comprising a polysulfide 500, a porous conducting material 100, a carbon fiber material 200 and a binder 300.
  • a porous conducting material 100, a carbon fiber material 200 and a binder 300 were provided, which were then subjected to a slurry forming step 12 with the addition of water.
  • the formed slurry was then subjected to a coating step 14 to form a preformed cathode host structure 400.
  • a sulfur source in fluid state 500 was then added to the preformed cathode host structure 400 to form the cathode material 600.
  • a prior art melt-diffusion method 20 of forming a cathode material 800 comprising elementary sulfur 700, a porous conducting material 100, a carbon fiber material 200 and a binder 300.
  • a porous conducting material 100 and elementary sulfur 700 were provided, which were then subjected to a melt-diffusion step 22 to impregnate the elementary sulfur 700 into the porous conducting material 100.
  • a carbon fiber material 200 and a binder 300 were added and subjected to a slurry forming step 24 with addition of water. The formed slurry was then subjected to a coating step 26 on a support to form the cathode material 800.
  • N-doped reduced graphene oxide was purchased from Nanjing JCNANO Technology Co. Ltd. (China). Vapor grown carbon fiber was purchased from Zhongke Leiming (Beijing) Science and Technology Co. Ltd. (China). LA-132 binder was purchased from Chengdu Indigo Power Sources Co. Ltd. (China). Sublimed sulfur (S), lithium sulfide (Li 2 S), dimethoxye thane (DME) and carbon disulphide (CS 2 ) were purchased from Sigma Aldrich (Singapore).
  • Samples for physisorption were prepared by removing cathode coated on an A1 current collector. The melt-diffused sulfur host cathode was washed several ti es with CS 2 to remove sulfur and dried under vacuum overnight before physisorption experiments. Elemental analysis of sulfur content was conducted on a Flashsmart elemental analyzer (Thermo Scientific).
  • the cathode formed in this example was prepared by Figure 1A and Figure IB.
  • the electrolyte was prepared by adding 1 M LiTFSI and 2 wt% LiN0 3 to a mixture of 1,3-dioxolane (DOL) and 1 ,2-dimethoxyethane (DME) (volume ratio of 1:1).
  • Li 2 S 6 (PS) solution was prepared by stirring a mixture of S (160.5 mg) and Li 2 S (46.0 mg) at 50°C in the electrolyte overnight in an Ar- filled glovebox.
  • Sulfur concentrations of 2.85 M and 5.42 M were prepared by adding 2 mL and 1 mL of electrolyte, respectively.
  • Sulfur cathode via sulfur vapor depsition was prepared by placing the preformed carbon scaffold on a stainless steel mesh of about 1 mm above a heated (175°C) reservoir of elemental sulfur for about 8 minutes corresponding to a sulfur loading density of about 1.5 mg cm 2 . Time can be prolonged to increase the sulfur loading.
  • Standard 2032-type coin cells were used for cell cycling and rate capability tests. Assembly was done in an argon-filled glovebox, with the 12.7-mm cathodes and lithium foil as the anode/reference electrode. A glass fiber membrane (GF/A, GE Healthcare) and a Celgard membrane, soaked with electrolyte, were used as separator. Both membranes were soaked with electrolyte. Galvanostatic charge-discharge cycling was conducted with a FAND CT2001 battery tester (Wuhan FAND electronics) between 1.6 V and 3.0 V i'v. Fi/Fi + for the rate capability studies and at a high sulfur loading of 5.05 mg cm 2 . For a sulfur loading of 1.50 mg cm 2 , fixed rate cycling was performed between 1.8 V and 2.8 V.
  • Cyclic voltammograms were obtained at a scan rate of 0.05 mV s -1 , and EIS was conducted at 10 mV at open circuit potential between 1 MHz and 0.01 Hz on an M204 Autolab potentiostat (Metrohm) fitted with a frequency response analyzer module.
  • the cathode material as prepared by the slurry coating method and sulfur vapor phase deposition showed similar specific capacities as compared to the cathode material as prepared by the slurry coating method and polysulfide solution addition. This indicates that the cathodes prepared by both methods are able to achieve high specific capacities and stability for lithium-sulfur battery performance due to the preformed cathode host structure.
  • PS/rGO cathode gave a higher initial (1220 vs. 1000 mAh g 1 ) and retained discharge capacity (999 vs. 780 mAh g 1 ) at a higher S loading (1.50 vs. 1.21 mg cm 2 ) and larger number of cycles (200 vs. 100), as compared to the Pt/graphene PS electrode, which showed the best performance amongst the previously reported slurry-coated PS cathodes (Table 1). [20]
  • the PS/rGO electrode could reach a practical areal capacity as LIB (4 mAh cm 2 ).
  • sulfur loading density was increased. Low sulfur utilization was expected at high sulfur loadings due to a thicker layer of insulating sulfur on the cathode surface.
  • the PS/rGO electrode gave an initial specific capacity of 858 mAh g 1 , corresponding to an areal capacity of 4.33 mAh cm 2 ( Figure 4c).
  • 798 mAh g 1 was retained, equivalent to an areal capacity of 4.03 mAh cm 2 .
  • the PS/rGO cathode is capable of achieving a practical areal capacity comparable to current LIB technology, and a superior electrochemical performance to other slurry-coated PS electrode.
  • Coulombic efficiencies are larger than 98% for both the PS/rGO cathode and the S/rGO cathode throughout the 200 cycles at 0.2, 0.5, 1.0 and 2.0 C, respectively.
  • Capacity fade known to be positively correlated with PS shuttling effect, was also determined for the two electrodes. Capacity fade values for the PS/rGO electrode were 0.100%, 0.080%, 0.091%, 0.075% per cycle at 0.2, 0.5, 1.0 and 2.0 C, respectively. For the S/rGO electrode, the capacity fade values were 0.142%, 0.117%, 0.105% and 0.106% per cycle at 0.2, 0.5, 1.0 and 2.0 C, respectively.
  • PS/rGO electrode showed a 48% higher specific capacity and 26% lower capacity fade per cycle, on average, than the S/rGO electrode.
  • the difference in electrochemical performance was found to be correlated to the difference in cathode structure.
  • the PS/rGO cathode was highly porous and interconnected before ( Figure 8a, b) and after cycling ( Figure 8c, d). The pores were uniform in size and evenly distributed, suggesting that the reversible reaction of Li-S system during battery cycling did not affect the porous structure of the PS/rGO cathode.
  • the difference in structure of the two electrodes was quantified by nitrogen adsorption which was performed on both cathodes in the absence of sulfur or Li-PS. Sulfur removal was necessary to simulate the effect of structural changes observed in SEM.
  • analysis was conducted on the preformed rGO cathode, whereas the S/rGO cathode was washed with CS 2 to remove the sulfur.
  • the nitrogen adsorption/desorption isotherm for both cathodes corresponded to a type II isotherm with H3 hysteresis loop ( Figure 10a).
  • the surface area and pore volume of the preformed rGO cathode were 264 m 2 /g and 0.31 cm 3 /g, respectively. These values were higher than that of the washed S/rGO cathode (181 m 2 /g and 0.25 cm 3 /g, respectively).
  • pore size distribution analysis revealed the presence of mesopores (3-4 nm) and macropores (60-90 nm) for both cathodes.
  • the rGO cathode had a comparable mesopore size (3.5 vs. 3.6 nm) and slightly larger macropore size (82 nm vs. 65 nm) than the washed S/rGO cathode.
  • the R e values of PS/rGO and S/rGO cells were found to be 4.7 W and 7.4 W, respectively.
  • the R CT values of PS/rGO and S/rGO cells are 3.0 W and 7.8 W, respectively. Since PS/rGO cathode has a higher surface area than the S/rGO cathode, the amount of electrochemically active sites would be greater in PS/rGO than S/rGO. Therefore, for the same amount of electrolyte, the insulating S layer would be thinner in PS/rGO than S/rGO, resulting in a lower resistance.
  • the cathode material can be used in a lithium-sulfur (Li-S) battery system for energy storage application. It offers potential advantages of high energy density, low material cost and high abundance of sulfur as compared to the conventional lithium battery.
  • the cathode material and the method of preparing the same provide a strong case towards a paradigm shift away from conventional cathode preparation approaches to improve the electrochemical performance of lithium- sulfur batteries.
  • the lithium-sulfur batteries that use the cathode material as described in the present disclosure may be used as high density power sources for a wide variety of applications for example in automobile (electric vehicles including electric cars, hybrid vehicles, electric bicycles, personal transporters and advanced electric wheelchairs, radio-controlled models, model aircraft, aircraft), portable devices (mobile phone/smartphone, laptops, tablets, digital cameras and camcorders), in power tools (including cordless drills, sanders, and saws), or in healthcare (portable medical equipment such as monitoring devices, ultrasound equipment, and infusion pumps).
  • automobile electric vehicles including electric cars, hybrid vehicles, electric bicycles, personal transporters and advanced electric wheelchairs, radio-controlled models, model aircraft, aircraft
  • portable devices mobile phone/smartphone, laptops, tablets, digital cameras and camcorders
  • power tools including cordless drills, sanders, and saws
  • healthcare portable medical equipment such as monitoring devices, ultrasound equipment, and infusion pumps.

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Abstract

L'invention concerne un matériau de cathode comprenant une couche d'espèces de soufre dispersées dans ou sur une matrice poreuse comprenant un premier matériau à base de carbone conducteur, un deuxième matériau à base de carbone conducteur et un liant, le deuxième matériau à base de carbone conducteur étant une fibre de carbone ou un nanotube de carbone. L'invention concerne également un matériau de cathode comprenant une couche d'espèces de soufre dispersées dans ou sur une matrice poreuse comprenant un premier matériau à base de carbone conducteur, un deuxième matériau à base de carbone conducteur et un liant, ladite matrice poreuse étant interconnectée avec des pores uniformes. L'invention concerne également des procédés de préparation du ou des matériaux de cathode susmentionnés.
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